US11655387B2 - Thermochromic pigment compositions - Google Patents

Thermochromic pigment compositions Download PDF

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US11655387B2
US11655387B2 US16/608,466 US201816608466A US11655387B2 US 11655387 B2 US11655387 B2 US 11655387B2 US 201816608466 A US201816608466 A US 201816608466A US 11655387 B2 US11655387 B2 US 11655387B2
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thermochromic pigment
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thermochromic
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Christelle DEBRAUWER
Anne-Lise Damiano
Alexander BOURQUE
Francois Foulonneau
Guillaume CHOLLET
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/18—Writing inks specially adapted for ball-point writing instruments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/17—Writing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials

Definitions

  • thermochromic pigment compositions containing specific compounds as a reactive environment.
  • This invention also regards thermochromic pigment microcapsules containing these thermochromic pigment compositions, ink compositions containing such thermochromic pigment microcapsules, and finally writing instruments containing such ink compositions.
  • thermochromic pigment compositions present reversable bleaching properties related to a change in temperature. These compositions are use when an ink marking requires repeated erasures.
  • thermochromic pigment compositions allowing the thermochromic pigment microcapsules to be prepared, presenting optimal condensation and crystallization temperatures that correspond respectively to the discoloration and recoloration temperatures of these compositions.
  • the compounds of the invention thus present numerous advantages to be used as the change regulator agent as well as several advantages to be used as a temperature change regulator agent in thermochromic inks: they present remarkable hysteresis characteristics and an extremely high contrast in color between the colored and discolored states.
  • the new compounds of the invention had the advantage of being able to be prepared through an ecological procedure, meaning from a recycled and bio-based product, 3-pentadecylphenol, taken from the waste of the production of cashew nuts.
  • thermochromic pigment containing:
  • X is preferably a single bond and Z preferably represents OCO.
  • y can be independently chosen among one of the following whole numbers: 0, 1, 2 or 3.
  • m can be independently chosen among one of the following whole numbers: 12, 13, 14, 15, 16, 17 or 18.
  • n can be independently chosen among one of the following whole numbers: 12, 13, 14, 15, 16, 17 or 18.
  • p can be independently chosen among one of the following whole numbers: 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18.
  • the compound (C) of the invention corresponds to the following formula (I a ):
  • X is a single bond
  • Z preferably represents OCO
  • y 0.
  • R 1 represents (CH 2 ) m CH 3 .
  • the compounds of formula (I) of the invention can be synthesized following four different synthesis pathways.
  • the first synthesis pathway responds to the following reactional diagram:
  • alcohol is solubilized with a catalyzer in an aprotic polar solvent, such as tetrahydrofuran (THF).
  • the catalyzer is preferably a volatile base like triethylamine.
  • the mixture is kept cold, at a temperature going from ⁇ 20 to 20° C., preferably from 0 to 20° C.
  • the mixture is kept cold in an ice bath or a solid CO 2 bath immersed in a solvent such as acetone or ethanol.
  • the mixture is advantageously rendered inert with the addition of nitrogen.
  • the acid chloride is then slowly added, preferably drop by drop, for a duration going from 15 to 60 minutes, preferably over 30 minutes.
  • the alcohol/acid chloride ratio used is preferably from 1.1/1 to 1/1.1 and ideally of 1/1.
  • the temperature is then increased to room temperature (25° C.), and the mixture is kept at this temperature for 1 to 3 hours, preferably for 2 hours, while stirring.
  • the compound of formula (I) obtained is then purified by recrystallization.
  • the second synthesis pathway corresponds to the following reactive diagram:
  • the alcohol has a condensation point lower than 60° C. and serves as a solvent. It is used in excess, preferably with an alcohol/carboxylic acid ratio of 1.5/1 to 3/1, and ideally of 2/1.
  • the alcohol and carboxylic acid mixture is heated in the presence of a catalyzer with a temperature ranging from 120 to 200° C., and preferably from 140 to 160° C., under reduced pressure, preferably from 200 to 800 mbar, until the acid is totally consumed.
  • the catalyzer is preferably a water-soluble acid, such as paratoluenesulfonic acid.
  • the compound of formula (I) obtained is then purified by recrystallization.
  • the third synthesis pathway corresponds to the following reactive diagram:
  • alcohol has a condensation point lower than 60° C. and acts as a solvent. It is used in excess, preferably with an alcohol/aromatic acid ratio of 1.5/1 to 3/1, and ideally of 2/1.
  • the mixture of alcohol and aromatic acid is heated in the presence of a catalyzer with a temperature ranging from 120 to 200° C., and preferably from 140 to 160° C., under reduced pressure, preferably from 200 to 800 mbar, until the acid is totally consumed.
  • the catalyzer is preferably a water-soluble acid, such as paratoluenesulfonic acid.
  • the compound of formula (I) is then purified by recrystallization.
  • the fourth synthesis pathway responds to the following reactive diagram:
  • alcohol is solubilized with a catalyzer in an aprotic polar solvent, such as tetrahydrofuran (THF).
  • the catalyzer is preferably of a volatile base, such as triethylamine.
  • the mixture is kept cold at a temperature ranging from ⁇ 20 to 20° C., preferably from 0 to 20° C.
  • the mixture is kept cold in an ice bath or a solid CO 2 bath immersed in a solvent such as acetone or ethanol.
  • the mixture is advantageously rendered inert with the addition of nitrogen.
  • Acid chloride is then added slowly, preferably drop by drop, for a duration going from 15 to 60 minutes, preferably 30 minutes.
  • the alcohol/acid chloride ratio used is preferably 1.1/1 to 1/1.1, and ideally of 1/1.
  • the temperature is then raised to room temperature (25° C.), and the mixture kept at this temperature for 1 to 3 hours, preferably for 2 hours, while stirred.
  • the compound of formula (I) obtained is then purified by recrystallization.
  • the compound of formula (I) of the invention is preferably chosen among the following compounds:
  • the compound of formula (I) of the invention can vary from 20 to 80° C., preferably from 30 to 80° C., and ideally from 40 to 70° C. It is this optimal condensation temperature that makes the compound of formula (I) of the invention an ideal compound that presents the required properties to be used as a temperature change regulator agent in the thermochromic pigment compositions.
  • thermochromic pigment composition of the invention the weight percentages of the compounds (A), (B), and (C) vary based on the nature and concentration of each of these compounds.
  • the weight percentage of the electron-donor dye compound (A) can vary from 1 to 10%, preferably from 1 to 6%, and ideally from 2 to 4%, by weight compared to the total weight of the thermochromic pigment composition.
  • the weight percentage of the electron-acceptor compound (B) can vary from 1 to 20%, preferably from 1 to 14%, and ideally from 4 to 10%, by weight with regard to the total weight of the thermochromic pigment composition.
  • the weight percentage of the compound (C) of formula (I) acting as a reactive environment can vary from 70 to 98%, preferably from 80 to 98%, and ideally from 86 to 94%, by weight with regard to the total weight of the thermochromic pigment composition.
  • thermochromic pigment composition of the invention can include:
  • (B) from 1 to 20%, preferably from 1 to 14%, and ideally from 4 to 10%, by weight of at least one electron-acceptor compound, and
  • thermochromic pigment composition of the invention includes:
  • thermochromic pigment composition of the invention presents a color-change hysteresis width ( ⁇ H) after encapsulation ranging from 20 to 80° C., preferably from 30 to 80° C., and ideally from 40 to 70° C.
  • an electron-donor organic compound dye (A) As an electron-donor organic compound dye (A), the traditionally known compounds such as the diphenylmethane phthalides, phenylindolyl phthalides, indolyphthalides, diphenylmethane azaphthalides, phenylindolyl azaphthalides, fluoranes, styrylquinolines and diazarhodamine lactones can be cited, two examples of these compounds being present below.
  • the electron-donor organic compound dye (A) can also be chosen from the 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide (Blue 63, CAS No.: 1552-42-7), the 2′-chloro-6′-(diethylamino)-3′-methylfluorane (Cas No.: 21121-62-0), 6′-(diethylamino)-1,3′-dimethylfluorane (Cas No.: 21934-68-9), 2-chloro-6-(diethylamino)-fluorane (CAS No.: 26567-23-7), 3-diathylaminobenzofluorane (CAS No.: 26628-47-7), 3′,6′-bis(diethylamino)-2-(4-nitrophenyl)spiro[isoindole-1,9′-xanthene
  • the electron-donor organic compound dye (A) is chosen from 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide (Blue 63, CAS No.: 69898-40-4) 2′-(dibenzylamino)-6′-(diethylamino)fluorane (CAS No.: 34372-72-0), N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridinyl]benzenamine (Yellow CK37, CAS No.: 144190-25-0), 7-(4-diethylamino-2-hexyloxyphenyl)-7-(1-ethyl-2-methyl-1H-indol-3-yl)-7H-furo[3,4-b]pyridine-5-one (Blue 203, CAS No.: 98660-18-5),
  • an electron-acceptor compound (B) we can provide a non-exhaustive list of the compounds with an active proton, such as the compounds with a phenolic hydroxyl group (monophenols or polyphenols), their derivatives that have substitutes, such as an alkyl group, an aryl group, an acyl group, an alcoxycarbonyl group, a carboxy group, their esters, an amido group or a halogen atom, and the condensed phenol-aldehyde resins such as bisphenols or trisphenols.
  • a phenolic hydroxyl group monophenols or polyphenols
  • their derivatives that have substitutes, such as an alkyl group, an aryl group, an acyl group, an alcoxycarbonyl group, a carboxy group, their esters, an amido group or a halogen atom
  • the condensed phenol-aldehyde resins such as bisphenols or trisphenols.
  • the electron-acceptor compound (B) can be chosen from the 2,2-bis-(4-hydroxy-3-methylphenyl)propane (Bisphenol C, CAS No.: 79-97-0), the 4-hexyl-1,3-dihydroxybenzene (4-hexylresorcinol, CAS No.: 136-77-6), 4,4′-cyclohexylidenebisphenol (BPZ, Cas No.: 843-55-0), 4,4′-(hexafluoroisopropylidene)diphenol (Bisphenol AF, CAS No.: 1478-61-1), 4,4′-(1-phenylethylidene)bisphenol (CAS No.: 1571-75-1), 2,2′-dihydroxybiphenyl (CAS No.: 1806-29-7), 4,4′-ethylidenebisphenol (CAS No.: 2081-08-5), 4,4′-(1,4-phenylenediisopropylidene)bisphenol
  • the electron-acceptor compound (B) is chosen among the 2,2-bis(4-hydroxy-3-methylphenyl)propane (Bisphenol C, CAS No.: 79-97-0), 4-hexyl-1,3-dihydroxybenzene (4-hexylresorcinol, CAS No.: 136-77-6), 4,4′-cyclohexylidenebisphenol (BPZ, CAS No.: 843-55-0), 4,4′-(hexafluroisopropylidene)diphenol (Bisphenol AF, CAS No.: 1478-61-1) 4,4′-(1-phenylethylidene)bisphenol (CAS No.: 1571-75-1), 2,2′-dihydroxybiphenyl (CAS No.: 1806-29-7), 4,4′-(1,4-phenylenedilsopropylidene) bisphenol (CCAS No.: 2167-51-3), 1,1-bis(4-hydroxy-3-methylphenyl)
  • thermochromic pigment composition of the invention is prepared by dissolving the compounds (A) and (B) in the compound (C) of the formula (I) of the invention, then stirring until a homogenous mixture is obtained, using a mixer like a homogenizer or a disperser.
  • thermochromic pigment composition of the invention is encapsulated in microcapsules to form thermochromic pigment microcapsules.
  • thermochromic pigment microcapsules have another purpose according to the invention. They have advantageous features in that they are resistant to mechanical restrictions, they are insoluble and therefore dispersible in water, and they agglomerate slowly.
  • thermochromic pigment microcapsules of the invention can vary from 20 to 80° C., preferably from 30 to 80° C., and ideally from 40 to 70° C.
  • the crystallization temperature (or recoloration temperature T1) of the thermochromic pigment microcapsules of the invention can vary from ⁇ 40 to 20° C., preferably from ⁇ 30 to 10° C., and ideally from ⁇ 20 to 0° C.
  • thermochromic pigment microcapsules of the invention have an average diameter ranging from 0.5 to 30 ⁇ m, preferably 1 to 10 ⁇ m, and ideally from 3-5 ⁇ m. This average diameter corresponds to d90 in volume and means that 90% of the volume of the microcapsules are made up of microcapsules with a size within the indicated interval. This average diameter can be determined by laser granulometry by using a Zetasizer Nano ZS device by Malvern Instruments.
  • micro-encapsulation procedures used include but are not limited to the conventional methods, such as:
  • thermochromic pigment microcapsules of the invention are advantageously based on amino resin, and preferably based on melamine resin, urea resin or benzoguanamine resin.
  • thermochromic pigment microcapsules of the invention are preferably prepared by in-situ polymerization from melamine resin.
  • thermochromic pigment microcapsules Another purpose of the invention regards an ink composition containing thermochromic pigment microcapsules according to the invention.
  • thermochromic pigment microcapsules of the invention present within the ink composition represent 5 to 50% by weight of the total weight of the ink composition.
  • the ink composition of the invention is largely composed of water.
  • water represents 40 to 80% by weight of the total weight of the ink composition.
  • the ink composition of the invention can also contain one or several water-miscible co-solvents.
  • the ink composition of the invention can contain an organic or aqueous solution, preferably an aqueous solvent.
  • solvents that can be added to the ink composition of the invention are water and water-miscible polar solvents, such as:
  • the solvents represent 5 to 20% by weight of the total weight of the ink composition.
  • the ink composition of the invention can also contain one or more specific adjuvants that can play different roles based on the final intended use. These uses can regard printing ink by serigraphy, offset printing, rotogravure printing, spray coating, electrostatic coating, electrodeposition coating, roll coating, inkjet printing, inks for writing tools like ballpoint pens, ink pens, markers and color pencils.
  • the ink composition of the invention can also be added to a thermoplastic resin composition or thermosetting composition to made molds.
  • An additional purpose of the invention regards writing instruments containing an ink composition according to the invention.
  • These instruments generally comprise a body containing the ink composition of the invention, and eventually a scrubbing agent.
  • the writing instrument according to the invention is favorably chosen from ballpoint pens, color pencils, chalk, and ideally chosen from friction erasable ballpoint pens.
  • the scrubbing element of the writing instrument is preferably an eraser.
  • the ink composition can be applied to paper, fibers, leather, plastic, glass, metal, wood, concrete.
  • the invention also includes other provisions that arise from the additional description below, which is connected to the synthesis of the formula compound (1) according to the invention, in their characterization and their use as a temperature change regulator agent in thermochromic pigment compositions.
  • the reactive environment is then extracted with 100 mL of ethyl acetate.
  • the organic phase is recovered and washed with three times 150 mL of water.
  • the organic phase is then dried on sodium sulphate and the solvent is evaporated.
  • the product is recrystallized twice by ethanol.
  • the analysis by gaseous-phase chromatography (GPC) of the product obtained shows that the product is 98% pure.
  • the reactive environment is kept at room temperature and is rendered inert by the addition of nitrogen. 10 g of palmitoyl chloride (CAS No. 112-67-4) are added drop by drop for 15 minutes. At the end of the addition, the reactive environment is stirred for 30 minutes at room temperature.
  • the reactive environment is then extracted with 100 mL of ethyl acetate.
  • the organic phase is recovered and washed with three times 150 mL of water.
  • the organic phase is then dried on sodium sulphate and the solvent is evaporated.
  • the product is recrystallized once by ethanol and once by isopropanol.
  • the analysis by gaseous-phase chromatography (GPC) of the product obtained shows that the product is 94% pure.
  • the reactive environment is then extracted with 100 mL of ethyl acetate.
  • the organic phase is recovered and washed with three times 150 mL of water.
  • the organic phase is then dried on sodium sulphate and the solvent is evaporated.
  • the product is recrystallized twice by ethanol.
  • the analysis by gaseous-phase chromatography (GPC) of the product obtained shows that the product is 98% pure.
  • the condensation temperatures T FUS of the compounds (1), (2) and (3) obtained are measured by differential scanning calorimetry (DSC) using a device TA Instruments Q20 on a temperature range going from ⁇ 50 to 100° C., at heating/cooling speeds of +/ ⁇ 20° C./minute. The temperatures measured are indicated in Table 1 below.
  • thermochromic pigment composition is prepared by mixing 2.2 parts by weight of 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide (compound (A), CAS No.: 69898-40-4), 2.2 parts by weight of 4,4′-(hexafluoroisopropylidene)diphenol (compound (B1) CAS No.: 1478-61-1), 2.2 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (compound (B2), CAS No.: 79-97-0), and 93.4 parts by weight of the compound (3) prepared beforehand (compound (C)):
  • the mixture obtained is heated and stirred at a temperature of 110° C. for 45 minutes, until the compounds (A), (B1) and (B2) are fully solubilized in the compound (C).
  • thermochromic pigment dispersed in an aqueous solvent A slurry formed of microcapsules of thermochromic pigment dispersed in an aqueous solvent is obtained, the microcapsules having a diameter d90 of 4.6 ⁇ m, determined using a Zetasizer Nano ZS system by Malvern Instruments with an illumination at 632 nm.
  • thermochromic pigment microcapsules obtained change color from blue to colorless above 48° C. with a color hysteresis effect.
  • thermochromic pigment microcapsules Change in color from color to colorless T1 (° C.) T2 (° C.) T3 (° C.) T4 (° C.) T H (° C.) T G (° C.) ⁇ H Thermochromic Blue ⁇ colorless 15 20 35 48 17 42 25 pigment microcapsules containing the compound (3)
  • the transition temperatures measured are the following:
  • T H T ⁇ ⁇ 1 + T ⁇ ⁇ 2 2
  • T S T ⁇ ⁇ 3 + T ⁇ ⁇ 4 3

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pens And Brushes (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US16/608,466 2017-04-27 2018-04-24 Thermochromic pigment compositions Active 2040-03-16 US11655387B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1753678A FR3065729B1 (fr) 2017-04-27 2017-04-27 Nouveaux composes de formule (i) et leur utilisation dans des compositions de pigment thermochrome
FR1753678 2017-04-27
PCT/FR2018/051032 WO2018197808A1 (fr) 2017-04-27 2018-04-24 Compositions de pigment thermochrome

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EP (1) EP3615507B1 (fr)
JP (1) JP2020517759A (fr)
CN (1) CN110650942A (fr)
AR (1) AR111732A1 (fr)
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US10563114B2 (en) * 2017-07-27 2020-02-18 Indian Oil Corporation Limited Corrosion inhibitor composition for pipelines
JP2020151932A (ja) * 2019-03-20 2020-09-24 株式会社リコー 感熱記録材料、感熱記録方法、感熱記録装置、及び感熱記録媒体
CN117085603B (zh) * 2023-10-18 2023-12-29 清华大学 一种实时监测运动副失效的方法

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2503701A (en) 1945-09-04 1950-04-11 Union Switch & Signal Co Simplexed line circuit system for remote-control systems
US4523207A (en) 1983-03-30 1985-06-11 Ncr Corporation Multiple copy thermal record sheet
US4720301A (en) * 1984-06-13 1988-01-19 Pilot Ink Co., Ltd. Reversible heat sensitive recording composition
US5876492A (en) 1997-09-23 1999-03-02 Xerox Corporation Ink compositions containing esters
WO2003060001A2 (fr) 2001-12-27 2003-07-24 Cytec Technology Corp. Olefines thermoplastiques stabilisees aux ultraviolets
WO2006002714A1 (fr) 2004-07-06 2006-01-12 Unilever Plc Composition de soin
WO2006044337A1 (fr) 2004-10-13 2006-04-27 Dow Global Technologies Inc. Formules de polymère de benzocyclobutène et méthodes de transformation desdites formules en milieu oxydant
US20110021678A1 (en) 2007-11-13 2011-01-27 Idemitsu Kosan Co., Ltd. Polycarbonate resin composition, molded polycarbonate resin, and process for producing the same
US20120202034A1 (en) 2011-02-03 2012-08-09 Jean-Francois Morizur Color and Heat Stable Polycarbonate Compositions and Methods of Making
US20120227623A1 (en) * 2009-09-24 2012-09-13 Kabushiki Kaisha Toshiba Erasable liquid ink
WO2013115800A1 (fr) 2012-01-31 2013-08-08 Chromatic Technologies, Inc. Systèmes thermochromiques ayant une hystérésis régulée
WO2015168389A1 (fr) 2014-05-01 2015-11-05 Cytec Industries Inc. Compositions stabilisantes permettant de stabiliser des matériaux contre la lumière ultraviolette et la dégradation thermique
CN105308150A (zh) 2013-06-14 2016-02-03 百乐墨水株式会社 感温变色性色彩记忆性组合物及内包有该组合物的感温变色性色彩记忆性微胶囊颜料
US20160089920A1 (en) 2013-05-13 2016-03-31 Fasver Thermochromic ink composition
CN105566736A (zh) 2016-01-27 2016-05-11 长园电子（东莞）有限公司 一种随温度变色示警的辐照交联聚烯烃热缩管
US20160333210A1 (en) * 2013-07-02 2016-11-17 Chromatic Technologies, Inc. Yellow Thermochromic Dyes, Inks Composition And Level Indicators
WO2016198784A1 (fr) 2015-06-12 2016-12-15 Ink And Out Sas Microcapsules et composition de maquillage ou de tatouage thermochromiques
US20190382585A1 (en) 2017-02-17 2019-12-19 Societe Bic Thermochromic pigment composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5833964A (en) * 1996-03-20 1998-11-10 Colgate-Palmolive Company Antiperspirant stick composition
JPH11166123A (ja) * 1997-08-05 1999-06-22 Pilot Ink Co Ltd 可逆的熱変色性を有する成形用樹脂組成物及びそれを用いた成形体
US6365629B1 (en) * 1999-05-10 2002-04-02 Alto, Inc. Fatty acid esters of aromatic alcohols and their use in cosmetic formulations
DE10226040A1 (de) * 2002-06-12 2003-12-24 Bayer Ag Verfahren zur Herstellung von Carbonsäurebenzylestern
CN1930005A (zh) * 2004-02-09 2007-03-14 太阳化学公司 可逆热致变色体系
JP5557432B2 (ja) * 2008-02-29 2014-07-23 パイロットインキ株式会社 可逆熱変色性水性インキ組成物及びそれを用いた筆記具、筆記具セット
JP5511259B2 (ja) * 2009-08-18 2014-06-04 パイロットインキ株式会社 可逆熱変色性水性インキ組成物及びそれを用いた筆記具、筆記具セット
CN105013414A (zh) * 2015-07-30 2015-11-04 苏州雄鹰笔墨科技有限公司 一种可逆温敏变色微胶囊、制备方法及其应用

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2503701A (en) 1945-09-04 1950-04-11 Union Switch & Signal Co Simplexed line circuit system for remote-control systems
US4523207A (en) 1983-03-30 1985-06-11 Ncr Corporation Multiple copy thermal record sheet
US4720301A (en) * 1984-06-13 1988-01-19 Pilot Ink Co., Ltd. Reversible heat sensitive recording composition
US5876492A (en) 1997-09-23 1999-03-02 Xerox Corporation Ink compositions containing esters
WO2003060001A2 (fr) 2001-12-27 2003-07-24 Cytec Technology Corp. Olefines thermoplastiques stabilisees aux ultraviolets
WO2006002714A1 (fr) 2004-07-06 2006-01-12 Unilever Plc Composition de soin
WO2006044337A1 (fr) 2004-10-13 2006-04-27 Dow Global Technologies Inc. Formules de polymère de benzocyclobutène et méthodes de transformation desdites formules en milieu oxydant
US20110021678A1 (en) 2007-11-13 2011-01-27 Idemitsu Kosan Co., Ltd. Polycarbonate resin composition, molded polycarbonate resin, and process for producing the same
US20120227623A1 (en) * 2009-09-24 2012-09-13 Kabushiki Kaisha Toshiba Erasable liquid ink
US20120202034A1 (en) 2011-02-03 2012-08-09 Jean-Francois Morizur Color and Heat Stable Polycarbonate Compositions and Methods of Making
WO2013115800A1 (fr) 2012-01-31 2013-08-08 Chromatic Technologies, Inc. Systèmes thermochromiques ayant une hystérésis régulée
US20160089920A1 (en) 2013-05-13 2016-03-31 Fasver Thermochromic ink composition
CN105308150A (zh) 2013-06-14 2016-02-03 百乐墨水株式会社 感温变色性色彩记忆性组合物及内包有该组合物的感温变色性色彩记忆性微胶囊颜料
EP3009493A1 (fr) 2013-06-14 2016-04-20 The Pilot Ink Co., Ltd Composition thermochromique à mémoire de couleur et pigment de microcapsule thermochromique à mémoire de couleur l'encapsulant
US9695329B2 (en) 2013-06-14 2017-07-04 The Pilot Ink Co., Ltd. Thermochromic color-memory composition and thermochromic color-memory microcapsule pigment encapsulating same
US20160333210A1 (en) * 2013-07-02 2016-11-17 Chromatic Technologies, Inc. Yellow Thermochromic Dyes, Inks Composition And Level Indicators
WO2015168389A1 (fr) 2014-05-01 2015-11-05 Cytec Industries Inc. Compositions stabilisantes permettant de stabiliser des matériaux contre la lumière ultraviolette et la dégradation thermique
WO2016198784A1 (fr) 2015-06-12 2016-12-15 Ink And Out Sas Microcapsules et composition de maquillage ou de tatouage thermochromiques
CN105566736A (zh) 2016-01-27 2016-05-11 长园电子（东莞）有限公司 一种随温度变色示警的辐照交联聚烯烃热缩管
US20190382585A1 (en) 2017-02-17 2019-12-19 Societe Bic Thermochromic pigment composition

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
Amorati et al, "Synthesis of new Cardonal and Cardo derivatives by allylation and regioselctive cyclocarbonylation reactions", Synthesis, No. 18, Jan. 1, 2002, Georg Thieme Verlag, Stuttgart, DE, pp. 2749-2755.
Chinese Office Action for related Chinese application No. 201880007865.7, 9 pages, dated Nov. 11, 2020.
International Search Report dated Aug. 10, 2018 for PCT application No. PCT/FR2018/051031.
International Search Report dated Aug. 16, 2018 in corresponding PCT application No. PCT/FR2018/051032, 2 pages.
International Search Report dated Aug. 23, 2018 in related PCT application No. PCT/FR2018/051033, 2 pages.
Japanese Office Action for related Japanese application No. 2019-537252, 5 pages, dated Mar. 9, 2022.
Japanese Office Action for related Japanese application No. 2019-537252, 5 pages, dated Oct. 11, 2021.
Kaufmann et al, "To know the Cashew-ole II about some derivatives of the main components of the shell folk". Jan. 1, 1967 (Jan. 1, 1967). pp. 577-579.
N. D. Ghatge, S. S. Mahajan and S. V. Vaidya, Secondary Plasticizers for Polyvinyl Chloride (PVC) Epoxidized Esters,Intern. J. Polymeric Muter., 1983, vol. 10, pp. 121-130 (Year: 1983). *

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